A variety of ketonitrones were synthesized in moderate to excellent yields with high chemo-, regio-, and stereoselectivity by using carbonyl-directed addition of N-alkylhydroxylamines to unactivated alkynes under mild conditions. The product diverisity could be controlled by the use of different bases, and EtN( n-Pr)2 could promote the formation of ketonitrones while using EtONa as base led to indanone-derived nitrones. Control experiments indicated that the carbonyl group of the substrate acted as an H-bond acceptor except for an electron-withdrawing group, and conjugated enone skeleton accounted for the high selectivity.